Method for production of a composite material using excess oxidant

ABSTRACT

A method of producing a composite material comprising: supplying a metal compound (M P C) of a product metal (M P ) and a reductant (R) capable of reducing the metal compound (M P C) of the product metal (MP) to a reactor; forming a composite material comprising a matrix of oxidised reductant (R 0 ) of the reductant (R), the product metal (M P ) dispersed in the matrix of oxidised reductant (R 0 ), and at least one of (i) one or more metal compounds (M P C R ) of the metal compound (M P C) in one or more oxidation states and (ii) the reductant (R); and recovering the composite material from the reactor, wherein the metal compound (M P C) of the product metal (M P ) is fed to the reactor such that it is in excess relative to the reductant (R).

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of International Application No.PCT/AU2016/050746, filed Aug. 12, 2016, which claims priority toAustralian Application No. 2015903277, filed Aug. 14, 2015, all of whichare incorporated herein by reference in their entirety.

FIELD OF INVENTION

The present invention relates to a method for the production of acomposite material via reduction-oxidation reaction with excess oxidant.In particular, the invention relates to a method for composite materialproduction in which at least one metal compound oxidant is fed to areactor in excess and reacted with at least one reductant to produce thedesired composite material from the at least one metal compound. Theinvention further provides methods for metal recovery from the compositematerial. The invention still further provides composite material formedby the method and metal subsequently recovered.

BACKGROUND ART

International Publication No. WO 2006/042360 provides a method forproducing titanium by reaction of titanium tetrachloride with magnesiumin a reactor, which may comprise a fluidised bed. The temperature in thereactor is above the melting point of magnesium, but below the meltingpoint of magnesium chloride. The method produces particles comprisingtitanium which are removed from the reactor and processed in order torecover titanium particles generally having a particle size of greaterthan 500 μm. Compliant with conventional thinking, the method of WO2006/042360 is operated under an excess of magnesium with unreactedmagnesium optionally collected and recycled to the reactor. This isunderstood to achieve complete conversion of TiCl₄ to titanium metal,while avoiding the formation of sub-chlorides, TiCl₂ and TiCl₃.

The present invention provides methods for producing a compositematerial from at least one metal compound in which an excess of oxidantis fed to the reactor during processing. The composite material willgenerally be in finely divided form and the method, generally, does notplace significant weight on the exclusion of by-products in thecomposite material. Metal recovered from the composite material maylikewise be in a finely divided form.

The subject matter claimed herein is not limited to embodiments thatsolve any disadvantages or that operate only in environments such asthose described above. Rather, this background is only provided toillustrate one exemplary technology area where some embodimentsdescribed herein may be practice.

SUMMARY OF INVENTION

As mentioned above, the present invention relates to a method forcomposite material production with excess oxidant being fed to thereactor during processing. More particularly, a method in which at leastone metal compound oxidant is fed to the reactor such that it is inexcess and is reacted with at least one reductant to produce the desiredcomposite material from the at least one metal compound is provided.

For convenience, the term “composite material” will be used to describea composite material that is a metal-salt composite, an alloy-saltcomposite or an inter-metallic-salt composite. That is, the term“composite material” as used herein is intended to include within itsscope a composite comprising a salt and (i) one metallic element, (ii)two or more metallic elements, or (iii) one or more metallic elementstogether with one or more non-metallic elements.

As used herein, reference to an “oxidant” includes within its scopemetal compounds (M_(P)C) that can be reduced by a reductant (R).Reference to a “reductant” includes within its scope a reductant (R)capable of reducing the metal compound (M_(P)C). Reference to “in excessrelative to the reductant (R)” includes within its scope excess of themetal compound (M_(P)C) relative to reductant that is expected to beavailable to be reduced in the prevailing conditions. For example, largeparticles of reductant may not be entirely available to be reduced inthe prevailing conditions.

According to one aspect of the invention there is provided a method ofproducing a composite material comprising:

-   -   supplying a metal compound (M_(P)C) of a product metal (M_(P))        and a reductant (R) capable of reducing the metal compound        (M_(P)C) of the product metal (M_(P)) to a reactor;    -   forming a composite material comprising a matrix of oxidised        reductant (R_(o)) of the reductant (R), the product metal        (M_(P)) dispersed in the matrix of oxidised reductant (R_(o)),        and at least one of (i) one or more metal compounds (M_(P)C_(R))        of the metal compound (M_(P)C) in one or more oxidation states        and (ii) the reductant (R); and    -   recovering the composite material from the reactor,    -   wherein the metal compound (M_(P)C) of the product metal (M_(P))        is fed to the reactor such that it is in excess relative to the        reductant (R).

The method of the invention therefore provides for the recovery ofcomposite material comprising the product metal (M_(P)) dispersed in amatrix of oxidised reductant (R_(o)) of the reductant (R), and at leastone of (i) one or more, for example reduced, metal compounds(M_(P)C_(R)) of the metal compound (M_(P)C) and (ii) the reductant (R).Where a reduced metal compound (M_(P)C_(R)) of the metal compound(M_(P)C) is present in the composite, this includes compounds of theproduct metal (M_(P)) in various oxidation states, such as sub-halidesof the metal compound (M_(P)C) of a product metal (M_(P)).

In preferred embodiments, the temperature within the reactor is suchthat the composite material maintains a finely divided particulate form,the temperature preferably being below the melting point of the oxidisedreductant (R_(o)) of the reductant (R), and further optionally above themelting point of the reductant (R). This embodiment will be discussed inmore detail below.

As used herein, the terms “temperature in the reactor” are intended tomean the average or bulk temperature of the reactor. There may belocalised “hot spots” within the reactor due to localisation ofexothermic reactions within the reactor. However, the temperaturesobserved at such “hot spots” should not be taken as being representativeof the reactor temperature.

For the avoidance of doubt, as used herein the terms “fed to the reactorsuch that it is in excess relative to the reductant (R)” is intended toinclude situations where the amount of metal compound (M_(P)C) of theproduct metal (M_(P)) fed to the reactor is in excess of stoichiometricequivalence relative to the amount of reductant (R) available forreaction in the reactor. Where more than one metal compound (M_(P)C) ofthe product metal (M_(P)) is fed to the reactor, the terms are intendedto include situations where the total amount of the metal compounds(M_(P)C) of the product metals (M_(P)) is in excess of stoichiometricequivalence relative to the amount of reductant (R) available forreaction in the reactor. Where more than one reductant (R) is fed to thereactor, the terms are intended to include situations where the amountof metal compound (M_(P)C) of the product metal (M_(P)) fed to thereactor is in excess of stoichiometric equivalence relative to theamount of the most electropositive of the reductants (R) available forreaction in the reactor. Where more than one metal compound (M_(P)C) ofthe product metal (M_(P)) is fed to the reactor and more than onereductant (R) is fed to the reactor, the terms are intended to includesituations where the total amount of the metal compounds (M_(P)C) of theproduct metals (M_(P)) is in excess of stoichiometric equivalencerelative to the amount of the most electrochemically positive of thereductants (R) available for reaction in the reactor.

Throughout this specification, unless the context requires otherwise,the word “comprise”, or variations such as “comprises” or “comprising”,will be understood to imply the inclusion of a stated step or element orinteger or group of steps or elements or integers, but not the exclusionof any other step or element or integer or group of steps, elements orintegers. Thus, in the context of this specification, the term“comprising” is used in an inclusive sense and thus should be understoodas meaning “including principally, but not necessarily solely”.

The metal compound (M_(P)C) of the product metal (M_(P)) (i.e. theoxidant) is fed to the reactor such that it is in excess relative to thereductant (R). This is contrary to previous teachings in the art, whichgenerally require addition of an excess of reductant. As discussedabove, an excess of reductant has conventionally been consideredadvantageous in order to ensure complete reduction of the metal compound(M_(P)C) to product metal (M_(P)), and also to eliminate the inclusionof reduced metal compounds (M_(P)C_(R)) of the metal compound (M_(P)C)in the product. According to the present invention, however, it has beenfound that advantages may be provided by ensuring an excess of metalcompound (M_(P)C) of the product metal (M_(P)) (i.e. oxidant) is fed tothe reactor. These advantages will be elucidated in more detail below.

The metal compound (M_(P)C) of the product metal (M_(P)) may be fed tothe reactor at any amount in excess of stoichiometric equivalencerelative to the reductant (R) available for reaction in the reactor. Ina preferred embodiment the molar ratio of metal compound (M_(P)C) of theproduct metal (M_(P)) to reductant (R) available for reaction in thereactor is 30:1, 15:1, 10:1, 5:1, 3:1, 2:1, 1.1:1, or 1.05:1.

In certain embodiments, it may be advantageous to recirculate excessmetal compound (M_(P)C) of the product metal (M_(P)) back to thereactor. In that case, it will be appreciated that the recirculatedmetal compound (M_(P)C) may be taken into account when considering thestoichiometric excess of the metal compound (M_(P)C) fed to the reactor.Specifically, it is envisaged that on recirculating of the metalcompound (M_(P)C) back to the reactor, the amount of new metal compound(M_(P)C) required for introduction to the reactor may be towards, orstoichiometrically equivalent to the amount of reductant (R) being fedto the reactor.

Generally, where the metal compound (M_(P)C) of the product metal(M_(P)) is volatile in the reactor, the residence time of the reductant(R) in the reactor will be substantially more than that of the metalcompound (M_(P)C) of the product metal (M_(P)). In this embodiment, thereductant (R) may have a residence time in the reactor that is from100-10,000 times the residence time of the metal compound (M_(P)C) ofthe product metal (M_(P)). In embodiments where the metal compound(M_(P)C) of the product metal (M_(P)) is a solid or liquid, theresidence time of the reductant (R) in the reactor may be substantiallythe same as that of the metal compound (M_(P)C) of the product metal(M_(P)).

The metal compound (M_(P)C) of the product metal (M_(P)) may beintroduced to the reactor in solid, liquid or vapour form. For example,it may be appropriate to feed a solid in situations where the metalcompound (M_(P)C) of the product metal (M_(P)) is a solid under theprevailing conditions in the reactor, such as where the metal compound(M_(P)C) of the product metal (M_(P)) comprises a chromium compound,such as chromium chloride, or the like. However, the metal compound(M_(P)C) of the product metal (M_(P)) is preferably in vapour or liquidform when fed to the reactor. In preferred embodiments the metalcompound (M_(P)C) of the product metal (M_(P)) is fed to the reactor atambient conditions, allowing heat exchange between the reactor and themetal compound (M_(P)C) of the product metal (M_(P)).

Generally, the reductant (R) is fed to the reactor as a solid, solidparticulate or molten liquid. The feed rate of the reductant (R) to thereactor will be somewhat dependent on the scale of the operation. Thefeed rate of the metal compound (M_(P)C) of the product metal (M_(P))may also depend on the scale of the operation.

As noted above, the method of the invention is considered suitable forthe production of composites comprising a single metallic element, twoor more metallic elements, and one or more metallic elements togetherwith one or more non-metallic elements. For example, the composites maycomprise an alloy or an inter-metallic as described above. In thatregard, the metal compound (M_(P)C) of the product metal (M_(P)) maycomprise a pnictogen compound or chalcogen compound. In preferredembodiments, the metal compound (M_(P)C) of the product metal (M_(P)) isa metal halide. Preferably, the metal halide is selected from the groupconsisting of halides of titanium, aluminium, vanadium, chromium,niobium, molybdenum, zirconium, silicon, boron, tin, hafnium, yttrium,iron, copper, nickel, bismuth, manganese, palladium, tungsten, cadmium,zinc, silver, cobalt, tantalum, scandium, ruthenium and the rare earthsor a combination of any two or more thereof.

According to a particularly preferred embodiment of the invention, themetal compound (M_(P)C) of the product metal (M_(P)) comprises TiCl₄. Inthis embodiment, the TiCl₄ is preferably in liquid form when fed to thereactor, although it may also be in vapour form.

The selection of the reductant (R) is not particularly limited. Inpreferred embodiments, the reductant (R) comprises a metal reductant(M_(R)) selected from the group consisting of Mg, Na, K, Li, Ba, Ca, Be,Al and any combination thereof, and any one or more thereof with anotherreductant (R′), although it is envisaged other options may also besuitable. In embodiments where two or more reductants (R), which mayinclude one or more metal reductant (M_(R)), are fed to the reactor, theamount of metal compound (M_(P)C) of the product metal (M_(P)) fed tothe reactor is in excess of stoichiometric equivalence relative to theamount of the most electrochemically positive of the reductants (R)available for reaction in the reactor. In other embodiments, it isthought that the reductant (R) may suitably comprise a multi-componentreductant, such as an alloy, for example an Mg—Al or Mg—Pd intermetallicor alloy, where some or all of the components participate inreduction-oxidation reactions in the process.

The temperature within the reactor is preferably such that the compositematerial maintains a finely divided particulate form. For example, thetemperature is preferably below the melting point of the oxidisedreductant (R_(o)) of the reductant (R). It may further be above themelting point of the reductant (R), although the method of the inventionmay work at lower temperatures. Advantageously, the reductant (R) isliquid in the reactor, while the oxidised reductant (R_(o)) is in solidform. In a preferred embodiment of the invention, the reductant (R)comprises magnesium and the temperature within the reactor is belowabout 714° C., for example from 650-714° C. It will be appreciated thatthe temperature within the reactor may be easily identified for otherreductants (R), such as metal reductants, depending on the melting pointof the oxidised reductant (R_(o)), and to a lesser extent the reductant(R), for a particular system.

The reactor may be any suitably configured apparatus in which the methodmay be carried out. For example, the reactor may be any type ofgas-solid contact device. In a preferred embodiment, the reactorcomprises a fluidised bed.

At least initially, the reactor may comprise seed particles or surfacesof the product metal (M_(P)), oxidised reductant (R_(o)) of thereductant (R), or other substrate material or a combination thereof. Thereactor may alternatively or additionally comprise other seed particlesor surfaces. For example, in some instances the seed particles orsurfaces may comprise a composite material as described herein. In apreferred embodiment, where the reactor comprises a fluidised bed, themethod may be self-seeding such that the method can be carried outcontinuously without the need to supply fresh seed particles or surfacesto the fluidised bed. The initial particle size of the seed particles ofthe fluidised bed is preferably from 10 μm to 2 mm, more preferably from50 μm to 500 μm. In another embodiment, the fluidised bed may have seedparticles or surfaces introduced continuously or periodically.

As noted above, the method of the invention may be used in theproduction of composite material comprising a single metallic elementand a salt of a single reductant. It is envisaged that this embodimentrepresents the most simplistic form of the method of the invention.

In other embodiments, however, the method of the invention will relateto more complex systems, for example in the production of an alloy-saltcomposite or inter-metallic-salt composite, or composites that includeone or more non-metallic components. In such systems, more than onecomponent may act as a reductant and two or more metal compounds(M_(P)C) of two or more product metals (M_(P)) may be fed to thereactor, and/or a non-metallic component may be additionally fed to thereactor.

According to certain embodiments of the invention, the product metal(M_(P)) is an alloy comprising two or more metallic elements and themethod comprises reacting metal compounds (M_(P)C) of each of the two ormore metallic elements with the reductant (R) in the reactor to reducethe metal compounds (M_(P)C) of each of the two or more metallicelements and recovering the composite material comprising the alloy ofthe two or more metallic elements.

In this embodiment, it will be appreciated that the reactions within thereactor will be more complex and will be dependent on theelectrochemical potential of the elements involved. In theseembodiments, the total amount of the metal compounds (M_(P)C) is inexcess relative to the reductant (R).

In these more complex systems, account must also be taken of thetemperature within the reactor. Generally, the temperature within thereactor is relatively close to or above the melting point of thereductant or any individual component of the reductant (R) and below themelting point of the most volatile oxidised reductant (R_(o)) componentof the reductant (R).

In a particularly preferred embodiment in which the product metal(M_(P)) is an alloy comprising two or more metallic elements, the two ormore metallic elements are selected from the group consisting oftitanium, aluminium and vanadium. According to this embodiment, themethod may comprise reacting two or more metal halides (M_(P)X) selectedfrom the group consisting halides of titanium, aluminium and vanadiumwith reductant (R) comprising magnesium, and recovering a metal-saltcomposite comprising an alloy of two or more metallic elements selectedfrom the group consisting of titanium, aluminium and vanadium and ahalide salt of magnesium. For example, the alloy may approximate Ti64alloy.

In that regard, it will be appreciated that Ti64 alloy generally refersto an alloy having a chemical composition of 6% aluminium, 4% vanadium,0.25% (maximum) iron, 0.2% (maximum) oxygen, and the remainder titanium.Ti64 is also commonly referred to as Grade 5 titanium.

In other embodiments, the method comprises supplying (i) at least onemetal compound (M_(P)C) of at least one of metallic element and (ii) atleast one other metallic or non-metallic component and the reductant (R)to the reactor and reducing the at least one metal compound (M_(P)C) ofthe at least one metallic element and recovering the composite materialcomprising the at least one metallic element of the at least one metalcompound (M_(P)C) and the at least one other metallic or non-metalliccomponent. For example, the additional component may comprise any one ormore of the groups consisting of beryllium, boron, carbon, nitrogen,oxygen, aluminium, silicon, phosphorous, sulphur, scandium, vanadium,chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium,germanium, arsenic, selenium, yttrium, zirconium, niobium, molybdenum,ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony,tellurium, hafnium, tantalum, tungsten, rhenium, osmium, iridium,platinum, gold, lead, bismuth, the Rare Earths and compounds thereof.

In certain embodiments other components, which may comprise additionalelements or compounds, may be included in the composite material byintroducing such components into the reactor. The method may thereforeadditionally comprise feeding metallic or other desirable components forinclusion in the composite material that are not expected to participatein reactions in the reactor. Additional components may be selected fromany element that is electrochemically more negative than any of theproduct metals (M_(P)). Where the product metal (M_(P)) is titanium,this may include by way of example an element selected from the groupconsisting of vanadium, chromium and nickel.

In one embodiment, palladium is incorporated into the compositematerial. In that regard, Grade 7 titanium contains 0.12 to 0.25%palladium. The small quantity of palladium provides enhanced crevicecorrosion resistance at low temperatures and high pH. Palladium may beadded to the composite material by, for example, introducing palladiumdirectly or as a component of the reductant (R) to the reactor. In thiscase, the palladium does not actually alloy with the metal product(M_(P)), rather it is an inclusion and passes through if added as ametal.

In certain embodiments, the composite material comprises unreactedreductant (R), for example up to 20 wt % reductant (R). The compositemay more generally comprise up to 3 wt % reductant (R), or may comprisea negligible amount of the reductant (R), or in more complex systems theleast electropositive component of the reductant (R). This is achievedthrough the use of an excess of oxidant in the reactor, whicheffectively reacts with the majority, if not all, of the reductant (R)in the reactor. As such, reductant (R) may not be present in the metalcomposite product produced in the reactor. This also provides additionaladvantages when compared with conventional processes in which excessreductant is seen in the reactor. That is, excess reductant does notaccumulate within the reactor, for example as pools or droplets ofmetal, or on the internal walls of the reactor. It has been found thatin cases where the reductant has appeared in the composite material,again, excess reductant has not accumulated within the reactor.

Following from this, according to another aspect of the invention thereis provided a composite material comprising:

-   -   a matrix of oxidised reductant (R_(o));    -   a product metal (M_(P)) dispersed in the matrix of oxidised        reductant (R_(o)); and    -   at least one of (i) one or more metal compounds (M_(P)C_(R)) of        the product metal (M_(P)) in one or more oxidation states,        and (ii) a reductant (R).

As noted above, the composite material may comprise up to 20 wt %, moregenerally 3 wt % of the reductant (R).

As with the previously described aspect of the invention, the productmetal (M_(P)) is preferably selected from the group consisting oftitanium, aluminium, vanadium, chromium, niobium, molybdenum, zirconium,silicon, boron, tin, hafnium, yttrium, iron, copper, nickel, bismuth,manganese, palladium, tungsten, cadmium, zinc, silver, cobalt, tantalum,scandium, ruthenium and the rare earths or a combination of any two ormore thereof. As such, in accordance with the definitions providedabove, the metal component may be an alloy of two or more metals. Incertain embodiments, the product metal (M_(P)) comprises at least two oftitanium, aluminium and vanadium.

The oxidised reductant (R_(o)) preferably comprises a metal halide(M_(R)X), for example MgCl₂, NaCl, KCl, LiCl, BaCl₂, CaCl₂, BeCl₂, AlCl₃or any combination thereof. In that regard, the reductant (R) may beselected from the group consisting of Mg, Na, K, Li, Ba, Ca, Be, Al andany combination thereof, and one or more thereof with another reductant(R′).

Referring to the above description, the method of the invention isconducted under an excess feed of oxidant. As such, the one or moremetal compounds (M_(P)C_(R)) of the product metal (M_(P)) in one or moreoxidation states may comprise one or more metal halides (M_(P)X) of themetal component (M_(P)).

The composite material may be in the form of particles. The particlesmay be spherical, or any shape. They may be regular or irregular inshape. The particles may have an average particle size of up to 500 μm,preferably from 20-300 μm. It is envisaged that desired shapes andparticle sizes of the particles may be advantageously generated bymanipulating the method of the invention, described above. In thatregard, we refer to the more detailed description of the invention thatfollows.

The metal component (M_(P)) within the composite material generally hasa particle size of up to about 1 micron. The surface area to volumeratio of the metal component (M_(P)) in the protective matrix ispreferably greater than 6 m²/mL.

In that regard, taking as an example where the composite material isformed by contacting Mg with an excess of TiCl₄ in a fluidised bedreactor to form Ti metal dispersed in a MgCl₂ matrix, it is thought thatat the extreme lower limit of particle size, one molecule of TiCl₄ mayreact with one atom of Mg and produce MgCl₂ and TiCl₂. Thereafter, onemore atom of Mg reacts with TiCl₂ and forms a second MgCl₂ and a singleTi atom. Therefore, at its limit, it is envisaged that the finelydivided metal component (M_(P)) may be present in the protective matrixof MgCl₂ on an atomic scale. Such examples would represent true “primaryparticles” of the metal component (M_(P)). In practice, there is theinherent desire on the part of the metal component (M_(P)) to nucleateor agglomerate (and possibly sinter), especially at nascent sites and inthe presence of some local heating, mixing, possible electronic transferthrough partially melted salt, etc. As such, it is considered that theremay be many atoms coalescing together to form the more realisticallyviable “primary particles” that would be observed under analysis. Theseparticles may be extremely small, for example on the nano-scale. At somepoint, however, further aggregation is not possible because, accordingto this embodiment at least, of “freezing” of the MgCl₂ to encapsulatethe Ti in its current state of agglomeration, resulting in a frozen seaof MgCl₂ with homogeneously dispersed titanium particles. Accordingly,in this particular embodiment, an ultrahigh surface area metal with nooxide barrier layer is completely protected from forming largerparticles or otherwise reacting unless the MgCl₂ is removed. However,when the protective matrix, in this case MgCl₂ is removed (for exampleby melting), the titanium particles are free to move around and furtheraggregate and form larger structures, such as shells of Ti. These may beconsidered “secondary particles”. It will be appreciated that thesecomments are equally relevant to the extreme upper limit of the surfacearea to volume ratio of the metal component (M_(P)) in the protectivematrix.

Another advantageous characteristic of the metal component (M_(P)) ofthese preferred embodiments of the invention is the lack of a protectiveoxide layer. The metal component (M_(P)) particles of these embodimentsdo not have an activation barrier, which correlates with a loweractivation energy (increase in reactivity) of the metal component(M_(P)). In addition to the above advantage, generally small particlesare highly pyrophoric. The composite material of the preferredembodiments of the invention is, comparatively, not. For conventionalmetal powders of approximately <10 μm, pyrophoricity becomes a majorissue, but can be serious even at much larger sizes (>100 μm) under someconditions. The protective matrix of the composite material of theinvention advantageously overcomes this issue.

According to a further aspect of the invention there is provided amethod of producing a product metal (M_(P)) comprising:

-   -   supplying a metal compound (M_(P)C) of a product metal (M_(P))        and a reductant (R) capable of reducing the metal compound        (M_(P)C) of the product metal (M_(P)) to a reactor, wherein the        metal compound (M_(P)C) of the product metal (M_(P)) is fed to        the reactor such that it is in excess relative to the reductant        (R);    -   forming a composite material comprising a matrix of oxidised        reductant (R_(o)) of the reductant (R), the product metal        (M_(P)) dispersed in the matrix of oxidised reductant (R_(o)),        and at least one of (i) one or more metal compounds (M_(P)C_(R))        of the metal compound (M_(P)C) in one or more oxidation states        and (ii) the reductant (R);    -   recovering the composite material from the reactor; and    -   removing the oxidised reductant (R_(o)) of the reductant (R),        and the reduced metal compound (M_(P)C_(R)) of the metal        compound (M_(P)C) and the reductant (R), if present, from the        composite material to recover the product metal (M_(P)).

The oxidised reductant (R_(o)) of the reductant (R) and reduced metalcompound (M_(P)C_(R)) of the metal compound (M_(P)C) and reductant (R),if present, may be removed from the composite material by any suitablemeans. For example, the oxidised reductant (R_(o)) of the reductant (R)and reduced metal compound (M_(P)C_(R)) of the metal compound (M_(P)C)may be removed from the composite material by solvent leaching.Preferably, the oxidised reductant (R_(o)) of the reductant (R) andreduced metal compound (M_(P)C_(R)) of the metal compound (M_(P)C) areremoved from the composite material by vacuum distillation.

In preferred embodiments, the method further comprises recovering thereductant (R). This may be achieved by any suitable means.

As discussed above, the temperature within the reactor is preferablyabove the melting point of the reductant (R) and below the melting pointof the oxidised reductant (R_(o)) of the reductant (R).

In certain embodiments, as discussed above, where the metal compound(M_(P)C) is a metal halide, the reduced metal compound (M_(P)C_(R)) ofthe metal compound (M_(P)C) may comprise one or more sub-halides of themetal compound (M_(P)C).

Various features and embodiments of this aspect of the invention may begleaned from the above description, which is incorporated herein in itsentirety. In that regard, the product metal (M_(P)) may comprisetitanium, aluminium, vanadium, chromium, niobium, molybdenum, zirconium,silicon, boron, tin, hafnium, yttrium, iron, copper, nickel, bismuth,manganese, palladium, tungsten, cadmium, zinc, silver, cobalt, tantalum,scandium, ruthenium and the rare earths or a combination of any two ormore thereof. Particular alloys of interest are those comprising atleast two metallic elements selected from the group consisting oftitanium, aluminium and vanadium. For example, the alloy may approximatea Ti64 alloy.

According to yet another aspect of the invention there is providedproduct metal (M_(P)) produced by the above described method ofproducing a product metal (M_(P)) according to the invention.

The product metal (M_(P)) may comprise particulate metal having aparticle size of less than 500 μm. Preferably the product metal (M_(P))comprises particulate metal having a particle size of up to 250 μm. Itis believed that the particulate metal may be suitable for use in manypowder metallurgical processes. In that regard, as mentioned above, itis envisaged that desired shapes and particle sizes of the particles maybe advantageously generated by manipulating the method of the invention.That is, the size and shape of the particles may be manipulated in orderto achieve suitable particles for a particular powder metallurgicalprocess.

The present invention consists of features and a combination of partshereinafter fully described and illustrated in the accompanyingdrawings, it being understood that various changes in the details may bemade without departing from the scope of the invention or sacrificingany of the advantages of the present invention.

BRIEF DESCRIPTION OF ACCOMPANYING DRAWINGS

To further clarify various aspects of some embodiments of the presentinvention, a more particular description of the invention will berendered by references to specific embodiments thereof, which areillustrated in the appended drawings. It should be appreciated thatthese drawings depict only typical embodiments of the invention and aretherefore not to be considered limiting on its scope. The invention willbe described and explained with additional specificity and detailthrough the accompanying drawings in which:

FIG. 1 illustrates a flow chart of a method for the production ofcomposite material, including additional illustration of options for thetreatment of the recovered composite material.

FIG. 2 shows a thermogram of the sample of Example 1 over the relevanttemperature range for the solid to liquid transition of magnesium.

FIG. 3 shows a thermogram of the sample of Example 2 over the relevanttemperature range for the solid to liquid transition of magnesium.

FIG. 4 shows a cross section of the metal particles following removal ofvolatile halides according to Example 8.

FIG. 5 shows the DTA thermogram of the composite particle of Example 9around the temperature of 650° C. exhibiting no endotherm to indicatethe presence of metallic magnesium.

FIG. 6 shows a thermogram of the composite product of Example 10surrounding the temperature of the melting point of aluminium of 660° C.

FIG. 7 shows a cross section of the metal particles of Example 10following removal of volatile halides.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, this specification will describe the present inventionaccording to the preferred embodiments. It is to be understood thatlimiting the description to the preferred embodiments of the inventionis merely to facilitate discussion of the present invention and it isenvisioned without departing from the scope of the appended claims.

Referring to FIG. 1, a flow chart of a method 100 for the recovery of acomposite material is illustrated. The flow chart also includesprocessing options 200 for the recovered composite material.

According to the method 100 for the recovery of a composite material,metal compound (M_(P)C) 110 of a product metal (M_(P)) and a reductant(R) 120 capable of reducing the metal compound (M_(P)C) 110 of theproduct metal (M_(P)) are supplied to a reactor 130. The amount of metalcompound (M_(P)C) 110 supplied to the reactor 130, including anyrecycled metal compound (M_(P)C) 140, is in excess relative to theamount of reductant 120 available for reaction in the reactor 130.Composite material 150 is recovered from the reactor 130. The compositematerial comprises a matrix of an oxidised reductant (R_(o)) of thereductant (R), the product metal (M_(P)) dispersed in the matrix, and atleast one of (i) a reduced metal compound (M_(P)C_(R)) of the metalcompound (M_(P)C) and (ii) the reductant (R).

The reactor 130, which will be discussed in terms of a fluidised bedreactor with reference to FIG. 1, is run at a temperature that maintainsthe finely divided form of the composite material. The temperature isbelow the melting point of the oxidised reductant (R_(o)) of thereductant (R) 120, which forms part of the composite material 150.Generally, the temperature may also be close to or above the meltingpoint of the reductant (R) 120. Where the temperature in the reactor 130is between the melting point of the reductant (R) 120 and the meltingpoint of the oxidised reductant (R_(o)), for example its oxidised salt,the reaction of the reductant (R) 120 with oxidant results in theformation of a composite material 150 comprised of largely or entirelysolid character. This ‘freezing’ reaction advantageously has the impactof creating finely divided and highly pure reaction products. Withoutseeking to be bound by theory, it is thought that the particle size ofthe composite material 150 is such that the finely divided elementscomprised within are sufficiently small that they interact differentlywith visible light than their bulk counterparts. For example, they mayappear black or dark in colour. The finely divided structure of thecomposite material 150 product has advantages compared to composites ofanalogous nominal compositions that do not have the same finely dividedstructure. These advantages will be elucidated in more detail below.

Where the reductant (R) 120 is fed into the reactor 130 as a solid orsolid particulate, the prevailing conditions in the reactor 130 ensure,with sufficient time, the melting of the reductant 120. The timerequired for melting of solid reductant 120 depends upon numerousfactors, including the feed mechanism, whether the reductant 120 is fedwith other materials, the temperature of the reactor 130, the reactionintensity of the reactor 130 per unit volume, the particulate density ofthe reductant 120 feed at any single location and, if other reductant orreagent or inert streams are in or are entering into the reactor, theproximity to these components and their respective temperatures whenimpinging on particles of the reductant 120.

The interaction of the reductant (R) 120 upon contacting other surfacesin the reactor 130 will depend on its phase at that time. If thereductant 120 particle is solid, it is possible the reductant 120particle will collide and rebound. It will then continue to interactwith other surfaces and environments in the reactor 130.

If the reductant 120 particle has a molten external surface and solidinner surface, it is possible the particle will adhere to any surface itimpacts, creating a composite of the two objects. The particle will thencontinue to interact with other surfaces and environments in the reactor130.

If the reductant 120 particle is molten when it interacts with othersurfaces, it may wet the surface. Depending upon the nature of thesolid-liquid interaction the thickness of the layer formed will vary. Itis considered that this may be manipulated through varying intensity ofinteractions, density of reductant 120 feed, temperature and time, etc.

Whether the end location of molten reductant in the reactor 130 is as astand-alone mass, wetted on a surface or combined with other surfaces,at some point it will generally interact with oxidant and react. At thispoint the thickness or the wetted layer or size of the molten mass orparticle is considered of some importance in determining the extent ofreaction of the reductant (R) 120 and the morphology of the finalcomposite material 150.

If the particle or wetted layer is sufficiently large or not completelymolten at this time, the freezing nature of the reaction as describedpreviously can result in a proportion of the reductant (R) becomingencapsulated by the composite material 150. Where the surface exposed tooxidant reacts to form a solid it may form a barrier (i.e. shell) thatmay restrict or eliminate the participation of the remaining reductantin further reduction. If the particle is sufficiently small or thewetted layer sufficiently thin, for example if the thickness of thereaction layer is equivalent to the radius of the particle or thethickness of the wetted layer, the process can consume the majority ifnot all of the reductant (R).

The amount of oxidant in the reactor relative to reductant (R) will bean important factor in determining the probability of the abovementioned interactions. Weighting of one form of interaction over otherscan be manipulated by changing operating conditions, feed forms, etc.The nature of surfaces in the reactor available for interaction,potential for sequential ordering and forms in which the reductant andoxidant are brought into contact can result in composites being formedwhich have diverse characteristics. These may include, withoutlimitation, excess or fully consumed reductant, layers of composite,layers of composite with magnesium interstitial layers. It is thoughtthat novel structured materials may be formed by sequential layering ofdissimilar layers of prescribed composition.

Once the composite material is recovered 150, it may be stored undersuitable conditions for later use, or may be processed 200 in variousways. The processing may include, without limitation, recovery of theproduct metal (M_(P)) 210, combining the composite material withcomposite material of other product metal (M_(P′)) 220, and/or othercompounding material (C_(M)) 230. As such, it is envisaged that variousproducts may be recovered, including without limitation product metal(M_(P)), an alloy or mixture of product metals (M_(P)/M_(P′)) 240, and amixture or composite product (M_(P)/C_(M)) 250. In any of these recoveryprocesses, it may also be desirable to recover reductant (R) andoptionally return this to the reductant feed 120.

The recovery of product from the composite materials of the presentinvention is described in detail in a co-pending International patentapplication with the title “METHOD FOR RECOVERY OF METAL-CONTAININGMATERIAL FROM A COMPOSITE MATERIAL”, filed on the same date as thepresent application. The content of the co-pending application isincorporated herein in their entirety.

EXAMPLES

The following examples are provided for exemplification only and shouldnot be construed as limiting on the invention in any way.

Example 1—Production of Titanium Metal Composite in the Presence ofExcess Oxidant with Unreacted Reductant Present in the Composite

A reaction vessel made from stainless steel was purged with high purityargon and heated externally to 680° C. The system was charged with 20kilograms of titanium composite particles as a seed material. The systemwas allowed to reach an internal temperature of 655° C. At this pointreactant feeds were introduced.

Titanium tetrachloride was supplied at a rate of 8 kilograms per hour.In this example the reductant phase was magnesium metal, supplied at arate of 2 kilograms per hour as a finely divided powder conveyed in alow volume of argon gas carrier stream entering the reactor. In theseproportions titanium tetrachloride is in excess by approximately 2.5 wt% relative to magnesium as the most electrochemically positive componentthat could be oxidised in the reactor.

The addition of the reactants to the reactor increased the temperaturein the reactor consistent with the exothermic nature of the reactions,reaching a steady bed temperature of 680° C. for an extended period.

The product stream from the reactor included free flowing black spheres(<3 mm diameter). Titanium tetrachloride was observed in the exhaust gasstream of the reactor.

The initial chemical composition of the bed is shown in the first lineTable 1 below. Samples from the product stream were taken hourly withcompositions of these shown in subsequent lines of Table 1.

The composition of the product is shown to be consistent and to containa relatively constant composition of titanium and magnesium asdetermined by XRF over a period of time. The composition of theseparticles indicates that they contain additional magnesium and lesstitanium than would be expected for stoichiometric reaction of titaniumtetrachloride and magnesium (20.4% Mg and 20.1% Ti) despite the presenceof excess oxidant. This indicates that the composite particles containat least some magnesium metal that was not oxidised.

FIG. 2 shows a thermogram of the sample over the relevant temperaturerange for the solid to liquid transition of magnesium. The endothermcentred at 650° C. confirms the presence of a quantity of unreactedmagnesium metal.

Heating of the composite particles from this run under prevailingconditions to remove the excess magnesium and magnesium chloride saltleft titanium metal particles.

TABLE 1 Titanium with constant excess Mg in composite Ti (total) Mg Mgin excess (wt %) (wt %) (%) 19.44 20.7 4.9 19.52 20.8 4.9 19.6 21.1 6.019.59 21.3 7.1 19.51 21.1 6.5 19.58 21 5.6 19.46 20.8 5.3 19.76 21 4.719.55 21 5.8 19.49 20.8 5.1 19.56 20.8 4.7 19.55 20.6 3.8 19.62 20.8 4.419.58 21.1 6.1 19.57 21.3 7.2 19.6 21.4 7.5 19.36 20.9 6.3 19.55 20.84.8 NOTE: Mg in excess = (wt % Mg/wt % Ti)/(2*MW(Mg)/MW(Ti))*100-100where the wt % of Ti and Mg is in all forms, metallic or oxidised asmeasured using a technique such as XRF.

Example 2—Production of Titanium Composite in the Presence of ExcessOxidant Demonstrating the Minimisation of Unreacted Reductant Present inthe Composite

A reaction vessel made from stainless steel was purged with high purityargon and heated externally to 680° C. The system was charged with 20kilograms of titanium composite particles as a seed material. The systemwas allowed to reach an internal temperature of 655° C. At this pointreactant feeds were introduced.

Titanium tetrachloride was supplied at a rate of 6.3 kilograms per hour.In this example the reductant phase was magnesium metal, supplied at arate of 1.5 kilograms per hour as a finely divided powder conveyed in alow volume of argon gas carrier stream entering the reactor. In theseproportions titanium tetrachloride is in excess by 7.5 wt % relative tomagnesium that could be oxidised in the reactor.

The addition of the reactants to the reactor increased the temperaturein the reactor consistent with the exothermic nature of the reactions,reaching a steady bed temperature of 680° C. for an extended period.

The product stream from the reactor included free flowing black spheres(<3 mm diameter). Titanium tetrachloride was observed in the exhaust gasstream of the reactor.

The initial chemical composition of the bed is shown in the first lineof Table 2. Samples from the product stream were taken hourly withcompositions of these shown in subsequent lines of Table 2.

The impact of a more significant excess of titanium tetrachloride fedinto the reactor than in example 1 is observed in the reduction ofunreacted magnesium being present in the composite particle samples overtime. The final composition of these particles indicates that theycontain very little to no additional magnesium than would be expectedfor stoichiometric reaction of titanium tetrachloride and magnesiumdespite the presence of excess oxidant.

FIG. 3 shows a thermogram of the sample over the relevant temperaturerange for the solid to liquid transition of magnesium. The absence of anendotherm centred around 650° C. confirms that no substantive unreactedmagnesium metal is present in the sample.

Heating of the composite particles from this run under prevailingconditions to remove the magnesium chloride and the little, if any,excess magnesium left titanium metal particles.

TABLE 2 Titanium with reducing excess Mg in composite to low levelTi(total) Mg Mg in excess (wt %) (wt %) (wt %) 19.80 20.63 2.6 19.7520.57 2.6 19.73 20.42 2.0 19.72 20.29 1.3 19.86 20.26 0.4 19.92 20.310.4 19.86 20.27 0.5 19.71 20.19 0.9 19.84 20.24 0.4

Example 3—Production of Titanium Composite in the Presence of ExcessOxidant Demonstrating the Formation of Larger Amounts of Sub-Halides

A reaction vessel made from stainless steel was purged with high purityargon and heated externally to 680° C. The system was charged with 20kilograms of titanium composite particles as a seed material. The systemwas allowed to reach an internal temperature of 655° C. At this pointreactant feeds were introduced.

Titanium tetrachloride was supplied at a rate of 7.3 kilograms per hour.In this example the reductant phase was magnesium metal, supplied at arate of 1.5 kilograms per hour as a finely divided powder conveyed in alow volume of argon gas carrier stream entering the reactor. In theseproportions titanium tetrachloride is in excess by approximately 25 wt %relative to magnesium fed into the reactor.

The addition of the reactants to the reactor increased the temperaturein the reactor consistent with the exothermic nature of the reactions,reaching a steady bed temperature of 680° C. for an extended period.

The product stream from the reactor included free flowing black spheres(<3 mm diameter). Titanium tetrachloride was observed in the exhaust gasstream of the reactor.

The initial chemical composition of the bed is shown in the first lineof Table 3. Samples from the product stream were taken hourly withcompositions of these shown in subsequent lines of Table 3.

The impact of a more significant excess of titanium tetrachloride fedinto the reactor than in example 2 is observed in the reduction ofmagnesium being present in the composite particle samples over time. Thefinal composition of these particles indicates that they contain lessmagnesium and more titanium than would be expected for thestoichiometric reaction of titanium tetrachloride and magnesium. Thetotal quantity of magnesium and titanium is also greater than would beexpected for the stoichiometric reaction of titanium tetrachloride andmagnesium, implying a reduction in total chlorine content of thecomposite. These factors all point to the composite containing increasedlevels of partially reduced titanium chlorides with little to nometallic magnesium.

Heating of the composite particles from this run under prevailingconditions to remove the excess magnesium chloride and partially reducedtitanium chlorides leaves behind titanium metal particles.

TABLE 3 Titanium with reducing excess Mg in composite until formation ofsubhalides Ti(total) Mg Mg in excess (wt %) (wt %) (wt %) 20.21 21.00152.3 20.04 22.159 8.9 20.2 21.2115 3.4 20.455 21.0395 1.3 20.375 20.6395−0.3 20.425 20.479 −1.3 20.41 20.341 −1.9 21.335 21.066 −2.8 20.69520.367 −3.1 20.24 20.1885 −1.8 20.615 20.258 −3.2 20.46 20.1065 −3.220.605 20.058 −4.1

Example 4—Titanium-Aluminium-Vanadium Composite

A reaction vessel made from stainless steel was purged with high purityargon and heated externally to 680° C. The system was charged with 200grams of titanium composite particles as a seed material. The system wasallowed to reach an internal temperature of 655° C. At this pointreactant feeds were introduced.

Titanium tetrachloride was supplied at a rate of 424 grams per hour,vanadium tetrachloride was supplied at a rate of 18 grams per hour andaluminium chloride was supplied at a rate of 36 grams per hour. In thisexample the reductant phase was magnesium metal, supplied at a rate of113 grams per hour as a finely divided powder conveyed in a low volumeof argon gas carrier stream entering the reactor. In these proportionsTiCl₄, VCl₄ and AlCl₃ are in excess by a total of 47% relative to theamount of magnesium that could be oxidised in the reactor.

The addition of the reactants to the reactor increased the temperaturein the reactor consistent with the exothermic nature of the reactions,reaching a steady bed temperature of 680° C. for an extended period.

The product stream, from the reactor included free flowing black spheres(<3 mm diameter). Metal halides were observed in the exhaust gas streamof the reactor.

A sample from the product stream was taken and subjected to heatingunder prevailing conditions to remove metal halides and any excessmagnesium leaving behind titanium-aluminium-vanadium containingparticles. This is shown in Table 4.

TABLE 4 Composition of metal component retained after removal ofvolatiles from Titanium-Aluminium-Vanadium composite. Sum Ti Mg Al V AsBi Co Cr Fe Mn (%) % % % % Ppm ppm ppm ppm ppm ppm <0.002 <0.002 <0.002<20 <20 <20 <20 <20 <20 99.0 91.1 0.11 2.24 4.93 <20 <20 55 790 3826 36899.0 91.2 0.10 2.22 4.87 <20 <20 28 759 3744 376 Sum Mo Na Nb Ni Pb Si YZr W Sn (%) Ppm ppm ppm ppm Ppm ppm ppm ppm Ppm Ppm <20 <20 <20 <20 <20<20 <20 <20 <50 <20 99.0 119 113 <20 779 <20 <20 <20 31 <20 n/a 99.0 11781 <20 738 <20 54 <20 23 <20 n/a

The ratios of metal compounds fed into the reactor were approximately90% Ti, 6% Al and 4% V on a metal mass basis. Despite this, the finalmetal composition of Ti 91%, Al 2.24% and V 4.93% indicates that eachdifferent halide has a differing conversion in the reactor. As such, tobe able to achieve a specific desired composition it is essential tofeed at least one oxidant in excess to drive the reduction-oxidationreactions to the desired degrees.

Example 5—Production of Vanadium Composite

A reaction vessel made from stainless steel was purged with high purityargon and heated externally to 680° C. The system was charged with 200grams of titanium composite particles as a seed material. The system wasallowed to reach an internal temperature of 655° C. At this pointreactant feeds were introduced.

Vanadium tetrachloride was supplied at a rate of 454 grams per. In thisexample the reductant phase was magnesium metal, supplied at a rate of95 grams per hour as a finely divided powder conveyed in a low volume ofargon gas carrier stream entering the reactor. In these proportionsvanadium tetrachloride is in excess relative to magnesium reductant thatcould be oxidised in the reactor.

The addition of the reactants to the reactor increased the temperaturein the reactor consistent with the exothermic nature of the reactions,reaching a steady bed temperature of 680° C. for an extended period.

The product stream from the reactor included free flowing black spheres(<3 mm diameter).

A sample from the product stream was taken and subjected to heatingunder prevailing conditions to remove metal halides and any excessmagnesium left predominantly vanadium containing particles. Thoseskilled in the art would appreciate that with more extended operationthat the titanium content of the composite particle and separated metalparticle reduces to below detection levels.

Example 6—Zirconium

A reaction vessel made from stainless steel was purged with high purityargon and heated externally to 680° C. The system was charged with 200grams of titanium composite particles as a seed material. The system wasallowed to reach an internal temperature of 655° C. At this pointreactant feeds were applied.

Zirconium tetrachloride was supplied at a rate of 211 grams per. In thisexample the reductant phase was magnesium metal, supplied at a rate of40 grams per hour as a finely divided powder conveyed in a low volume ofargon gas carrier stream entering the reactor. In these proportionszirconium tetrachloride is in excess relative to magnesium reductant fedinto the reactor.

The addition of the reactants to the reactor increased the temperaturein the reactor consistent with the exothermic nature of the reactions,reaching a steady bed temperature of 680° C. for an extended period.

The product stream from the reactor included free flowing black spheres(<3 mm diameter). Zirconium tetrachloride was observed in the exhaustgas stream of the reactor.

A sample from the product stream was taken and subjected to heatingunder prevailing conditions to remove metal halides and any excessmagnesium left predominantly zirconium containing particles. Thoseskilled in the art would appreciate that with more extended operationthat the titanium content of the composite particle and separated metalparticle reduces to below detection levels.

Example 7—Ti—Al Composite with Mg as Reductant

A reaction vessel made from stainless steel was purged with high purityargon and heated externally to 680° C. The system was charged with 200grams of titanium composite particles as a seed material. The system wasallowed to reach an internal temperature of 655° C. At this pointreactant feeds were applied.

Titanium tetrachloride was supplied at a rate of 424 grams per andaluminium chloride was supplied at a rate of 148 grams per hour. In thisexample the reductant phase was magnesium metal, supplied at a rate of102 grams per hour as a finely divided powder conveyed in a low volumeof argon gas carrier stream entering the reactor. In these proportionsoxidant halides are in excess relative to magnesium reductant fed intothe reactor.

The addition of the reactants to the reactor increased the temperaturein the reactor consistent with the exothermic nature of the reactions,reaching a steady bed temperature of 680° C. for an extended period.

The product stream from the reactor included free flowing black spheres(<3 mm diameter). Oxidant halides were observed in the exhaust gasstream of the reactor.

A sample from the product stream was taken and subjected to heatingunder prevailing conditions to remove metal halides and any excessmagnesium leaving behind titanium-aluminium containing particles. Thecomposition of the sample is shown in Table 5.

TABLE 5 Titanium-Aluminide Sum Ti Mg Al V As Bi Co Cr Fe Mn (%) % % % %ppm ppm ppm ppm ppm ppm <0.002 <0.002 <0.002 <20 <20 <20 <20 <20 <2095.4 82.4 0.17 12.6 0.01 58 <20 122 192 1578 629 Sum Mo Na Nb Ni Pb Si YZr W Sn (%) ppm Ppm ppm ppm ppm ppm ppm ppm ppm Ppm <20 <20 <20 <20 <20<20 <20 <20 <50 <20 95.4 <20 <20 <20 87 <20 215 <20 53 <20 n/a

Example 8—Production of Titanium Metal Composite in the Presence ofExcess Oxidant with Unreacted Reductant Present in the Composite Belowthe Melting Point of the Reductant

A reaction vessel made from stainless steel was purged with high purityargon and heated externally to 525° C. The system was charged with 2kilograms of titanium composite particles as a seed material. The systemwas allowed to reach an internal temperature of 520° C. At this pointreactant feeds were introduced.

Titanium tetrachloride was supplied at a rate of 1.2 kilograms per hour.In this example the reductant phase was magnesium metal, supplied at arate of 300 grams per hour as a finely divided powder with a particlesize between 50-63 μm and was conveyed in a low volume of argon gascarrier stream entering the reactor. In these proportions titaniumtetrachloride is in excess by approximately 3.5 wt % relative tomagnesium as the most electrochemically positive component that could beoxidised in the reactor.

The addition of the reactants to the reactor increased the temperaturein the reactor consistent with the exothermic nature of the reactions,reaching a steady bed temperature of 550° C. for an extended period.

The product stream from the reactor included free flowing black spheres(<3 mm diameter). Titanium tetrachloride was observed in the exhaust gasstream of the reactor.

Under these conditions the reductant is solid and the oxidant is avapour. This limits the reactivity of the reductant where the exteriorshell of reductant particles reacts (˜10-20 μm) based on each particlesresidence time in the reactor. As such, the core of reductant particlesgreater than the reaction shell remains in metallic form.

Heating of the composite particles from this run under prevailingconditions to remove the excess magnesium and magnesium chloride saltleft titanium metal particles. The mass fraction of metal product tocomposite during this process is 16%.

FIG. 4 shows a cross section of the metal particles following removal ofvolatile halides. It can be seen that the particles have a wallthickness of 10-20 μm and a hollow core of 20-40 μm. It is consideredthat the hollow core would have contained metallic magnesium prior toremoval of volatiles. The composition of the bright phase is essentially100% titanium.

This example shows that only a limited shell thickness of magnesium hasbeen reacted and exemplifies the definition of the reductant to onlyinclude the material which is capable of being reduced in the prevailingconditions.

Example 9—Very High Excess of TiCl₄

A reaction vessel made from stainless steel was purged with high purityargon and heated externally to 525° C. The system was charged with 2kilograms of titanium composite particles as a seed material as derivedfrom the conditions prevailing from Example 8. The system was allowed toreach an internal temperature of 520° C. At this point reactant feedswere introduced.

Titanium tetrachloride was supplied at a rate of 1.2 kilograms per hour.In this example the reductant phase was magnesium metal, supplied at arate of 10 grams per hour as a finely divided powder with a particlesize between 50-63 μm and conveyed in a low volume of argon gas carrierstream entering the reactor. In these proportions titanium tetrachlorideis in excess by approximately 3000 wt % relative to magnesium as themost electrochemically positive component that could be oxidised in thereactor.

The addition of the reactants to the reactor increased the temperaturein the reactor consistent with a mild exothermic reaction, reaching asteady bed temperature of 530° C. Over a period of time the bedtemperature reduced towards the starting temperature prior to feedsbeing introduced.

The product stream from the reactor included free flowing black/greenspheres (<3 mm diameter). A significant quantity of titaniumtetrachloride was observed in the exhaust gas stream of the reactor. Themass of material discharged from the reactor to maintain a constantreactor mass was greater than that would be expected for the conversionof the magnesium fed into the reactor if converted into compositematerial. This implies that titanium tetrachloride was beingincorporated into the composite particles by reacting with compoundsother than the fed magnesium.

Under these conditions the reductant is solid and the oxidant is avapour. The feed rate of reductant into the reactor relative to the bedsize increases the residence time significantly, providing a greatertime for reactions to occur and the extent of reaction to increase,including for magnesium in the seed bed to be converted.

FIG. 5 shows the DTA thermogram of the composite particle around thetemperature of 650° C. exhibiting no endotherm to indicate the presenceof metallic magnesium.

Heating of the composite particles from this run under prevailingconditions to remove the excess magnesium and magnesium chloride saltleft titanium metal particles. The mass fraction of metal product tocomposite during this process is 12%.

The combination of no metallic magnesium in the composite and reducedmetallic mass retained after removal of volatiles indicates an enhancedlevel of reaction of solid phase magnesium beyond the surface 10-20 μmwith longer residence time in conditions of significant excess ofoxidant. Also the formation of a significant portion of sub-halidespresent in the composite particle can be similarly confirmed.

Example 10—Aluminium as a Reductant

A reaction vessel made from stainless steel was purged with high purityargon and heated externally to 200° C. The system was charged with 2kilograms of titanium composite particles formed under similarconditions previously as a seed material. The system was allowed toreach an internal temperature of 190° C. At this point reactant feedswere introduced.

Titanium tetrachloride was supplied at a rate of 1.2 kilograms per hour.In this example the reductant phase was aluminium metal, supplied at arate of 150 grams per hour as a finely divided powder with a d₅₀particle size of around 25 μm and was conveyed in a low volume of argongas carrier stream entering the reactor. In these proportions titaniumtetrachloride is in excess by approximately 50 wt % relative toaluminium as the most electrochemically positive component that could beoxidised in the reactor.

The addition of the reactants to the reactor increased the temperaturein the reactor consistent with a minor exothermic nature of thereactions, reaching a steady bed temperature of 215° C. for an extendedperiod.

The product stream from the reactor included fine black/grey particles(<1 mm diameter). Titanium tetrachloride was observed in the exhaust gasstream of the reactor.

Under these conditions the reductant is solid and the oxidant is avapour. Also, the oxidised reductant (AlCl₃) is notionally a vapour atthis temperature also and not available to form a part of the protectivematrix for the reduced metal. In this example the titanium subhalidesform part of the composite particle protective matrix.

FIG. 6 shows a thermogram of the composite product surrounding thetemperature of the melting point of aluminium of 660° C. A clearendotherm is observed indicating the presence of metallic aluminiumconsistent with analogous result in example 9. Exotherms are observedabove and below the melting point of aluminium which are consistent withthe formation of titanium aluminides.

FIG. 7 shows a cross section of the metal particles following removal ofvolatile halides. The composition of the bright phase is 63% Aluminiumand 27% Titanium, consistent with TiAl₃.

While the above examples primarily employ magnesium metal as thereductant, those in the art will appreciate that other metals, includingbut not limited to sodium, potassium, lithium and barium, would beexpected to achieve similar results given their similar properties.

Unless the context requires otherwise or specifically stated to thecontrary, integers, steps or elements of the invention recited herein assingular integers, steps or elements clearly encompass both singular andplural forms of the recited integers, steps or elements.

It will be appreciated that the foregoing description has been given byway of illustrative example of the invention and that all suchmodifications and variations thereto as would be apparent to persons ofskill in the art are deemed to fall within the broad scope and ambit ofthe invention as herein set forth.

1. A method of producing a composite material comprising: supplying ametal compound (M_(P)C) of a product metal (M_(P)) and a reductant (R)capable of reducing the metal compound (M_(P)C) of the product metal(M_(P)) to a reactor; forming a composite material comprising a matrixof oxidised reductant (R_(o)) of the reductant (R), the product metal(M_(P)) dispersed in said matrix of oxidised reductant (R_(o)), and atleast one of (i) one or more metal compounds (M_(P)C_(R)) of the metalcompound (M_(P)C) in one or more oxidation states and (ii) the reductant(R); and recovering the composite material from the reactor, wherein themetal compound (M_(P)C) of the product metal (M_(P)) is fed to thereactor such that it is in excess relative to the reductant (R).
 2. Amethod according to claim 1, wherein the temperature within the reactoris such that the composite material maintains a finely dividedparticulate form, the temperature preferably being below the meltingpoint of the oxidised reductant (R_(o)) of the reductant (R), andfurther optionally above the melting point of the reductant (R).
 3. Amethod according to claim 1, wherein the molar ratio of metal compound(M_(P)C) of the product metal (M_(P)) to reductant (R) fed to thereactor is 30:1, 15:1, 10:1, 5:1, 3:1, 2:1, 1.1:1, or 1.05:1.
 4. Amethod according to claim 1, wherein unreacted metal compound (M_(P)C)of said product metal (M_(P)), on leaving said reactor, is recirculatedto said reactor.
 5. A method according to claim 1, wherein the metalcompound (M_(P)C) of the product metal (M_(P)) is volatile in thereactor and said reductant metal (M_(R)) has a residence time in saidreactor that is from 100-10,000 times the residence time of said metalcompound (M_(P)C) of said product metal (M_(P)).
 6. A method accordingto claim 1, wherein said reductant (R) is selected from the groupconsisting of Mg, Na, K, Li, Ba, Ca, Be, Al and any combination thereof,and any one or more thereof with another reductant (R′).
 7. A methodaccording to claim 1, wherein said metal compound (M_(P)C) of saidproduct metal (M_(P)) is in vapour or liquid form when fed to saidreactor.
 8. A method according to claim 1, wherein said reductant (R)comprises magnesium and the temperature within said reactor is such thatthe composite material maintains a finely divided particulate form, thetemperature preferably being below about 714° C., for example from 650to 714° C.
 9. A method according to claim 1, wherein, at leastinitially, said reactor comprises seed particles or surfaces of theproduct metal (M_(P)), oxidised reductant (R_(o)) of the reductant (R),or other substrate material or a combination thereof.
 10. A methodaccording to claim 1, wherein the product metal (M_(P)) is an alloycomprising two or more metallic elements and the method comprisessupplying metal compounds (M_(P)C) of each of the two or more metallicelements and the reductant (R) to the reactor and reducing the metalcompounds (M_(P)C) of each of the two or more metallic elements andrecovering the composite material comprising the alloy of the two ormore metallic elements.
 11. A method according to claim 10, wherein thetotal amount of the metal compounds (M_(P)C) is in excess relative tothe reductant (R).
 12. A method according to claim 1, wherein saidmethod comprises supplying (i) at least one metal compound (M_(P)C) ofat least one of metallic element and (ii) at least one other metallic ornon-metallic component and the reductant (R) to the reactor and reducingthe at least one metal compound (M_(P)C) of the at least one metallicelement and recovering the composite material comprising the at leastone metallic element of the reduced at least one metal compound (M_(P)C)and the at least one other metallic or non-metallic component.
 13. Amethod according to claim 1, wherein said composite material comprisesunreacted reductant (R) is present in an amount of up to 20 wt %.
 14. Acomposite material comprising: a matrix of oxidised reductant (R_(o)); aproduct metal (M_(P)) dispersed in said matrix of oxidised reductant(R_(o)); and at least one of (i) one or more metal compounds(M_(P)C_(R)) of said product metal (M_(P)) in one or more oxidationstates, and (ii) a reductant (R).
 15. A composite material according toclaim 14, wherein said composite material comprises up to 20 wt % ofsaid reductant (R).
 16. A composite material according to claim 14,wherein said product metal (M_(P)) is selected from the group consistingof titanium, aluminium, vanadium, chromium, niobium, molybdenum,zirconium, silicon, boron, tin, hafnium, yttrium, iron, copper, nickel,bismuth, manganese, palladium, tungsten, cadmium, zinc, silver, cobalt,tantalum, scandium, ruthenium and the rare earths or a combination ofany two or more thereof.
 17. A composite material according to claim 16,wherein said product metal (M_(P)) comprises at least two of titanium,aluminium and vanadium.
 18. A composite material according to claim 14,wherein said oxidised reductant (R_(o)) comprises a metal halide(M_(R)X) selected from the group consisting of MgCl₂, NaCl, KCl, LiCl,BaCl₂, CaCl₂, BeCl₂, AlCl₃ and any combination thereof.
 19. A compositematerial according to claim 14, wherein said reductant (R) is selectedfrom the group consisting of Mg, Na, K, Li, Ba, Ca, Be, Al and anycombination thereof, and any one or more thereof with another reductant(R′).
 20. A composite material according to claim 14, wherein said oneor more metal compounds (M_(P)C_(R)) of said product metal (M_(P)) inone or more oxidation states comprise one or more metal halides (M_(P)X)of said metal component (M_(P)).
 21. A composite material according toclaim 14, wherein said composite material is in the form of particleshaving an average particle size of up to 500 μm, preferably from 20-300μm.
 22. A method of producing a product metal (M_(P)) comprising:supplying a metal compound (M_(P)C) of a product metal (M_(P)) and areductant (R) capable of reducing the metal compound (M_(P)C) of theproduct metal (M_(P)) to a reactor, wherein the metal compound (M_(P)C)of the product metal (M_(P)) is fed to the reactor such that it is inexcess relative to the reductant (R); forming a composite materialcomprising a matrix of oxidised reductant (R_(o)) of the reductant (R),the product metal (M_(P)) dispersed in said matrix of oxidised reductant(R_(o)), and at least one of (i) one or more metal compounds(M_(P)C_(R)) of the metal compound (M_(P)C) in one or more oxidationstates and (ii) the reductant (R); recovering the composite materialfrom the reactor; and removing the oxidised reductant (R_(o)) of thereductant (R), and the reduced metal compound (M_(P)C_(R)) of the metalcompound (M_(P)C) and the reductant (R), if present, from the compositematerial to recover the product metal (M_(P)).
 23. Product metal (M_(P))produced by a method of claim 22, wherein said product metal (M_(P))comprises particulate metal having a particle size of less than 500 μm,preferably from 20-300 μm.
 24. A method of producing a solid compositematerial comprising: continuously supplying a metal compound (M_(P)C) ofa product metal (M_(P)) and a reductant (R) capable of reducing themetal compound (M_(P)C) of the product metal (M_(P)) to a reactor;forming in the reactor a solid composite material comprising a matrix ofoxidised reductant (R_(o)) of the reductant (R), the product metal(M_(P)) dispersed in said matrix of oxidised reductant (R_(o)), and atleast one of (i) one or more metal compounds (M_(P)C_(R)) of the metalcompound (M_(P)C) in one or more oxidation states and (ii) the reductant(R); and recovering the solid composite material from the reactor,wherein the metal compound (M_(P)C) of the product metal (M_(P)) is fedto the reactor such that it is in excess relative to the reductant (R).